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Methanesulfonic Acid → (5-Fluoro-4-methyl-pyrimidin-2-yl)-[3-methyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-amine

HRID 1039896
ノート
印刷プレビュー

反応式

HRID 1039896 の反応式
Cl[C:2]1[N:7]=[C:6]([CH3:8])[C:5]([F:9])=[CH:4][N:3]=1.[CH3:10][C:11]1[CH:12]=[C:13]([NH2:26])[CH:14]=[C:15]([B:17]2[O:21][C:20]([CH3:23])([CH3:22])[C:19]([CH3:25])([CH3:24])[O:18]2)[CH:16]=1.CS(O)(=O)=O>O1CCOCC1.C([O-])(O)=O.[Na+]>[F:9][C:5]1[C:6]([CH3:8])=[N:7][C:2]([NH:26][C:13]2[CH:14]=[C:15]([B:17]3[O:21][C:20]([CH3:22])([CH3:23])[C:19]([CH3:25])([CH3:24])[O:18]3)[CH:16]=[C:11]([CH3:10])[CH:12]=2)=[N:3][CH:4]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

6

反応物 3

HCID 6395Methanesulfonic AcidHCID 207780732-Chloro-5-fluoro-4-methylpyrimidineHCID 672361713-Methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline

生成物 1

HCID 58456078(5-Fluoro-4-methyl-pyrimidin-2-yl)-[3-methyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-amine収率 62.6%

試薬・触媒・溶媒 2

HCID 312751,4-Dioxane
溶媒
HCID 516892Sodium Bicarbonate溶媒

反応条件

温度
100 °C

実験手順

To a solution of 2-chloro-5-fluoro-4-methyl-pyrimidine (4.00 g, 27.3 mmol) and 3-methyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenylamine (8.27 g, 35.5 mmol) in dioxane (40.7 mL) was added methanesulfonic acid (1.77 ml, 27.3 mmol) dropwise during which the reaction exothermed 15.7° C. Subsequently the reaction mixture was heated to 100° C. and allowed to stir over the weekend. The mixture was cooled to room temperature and was diluted with saturated aqueous NaHCO3 and extracted with ethyl acetate. The organic extracts were washed with brine and dried over MgSO4, filtered and concentrated in vacuo. Purification by flash chromatography provided (5-fluoro-4-methyl-pyrimidin-2-yl)-[3-methyl-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-amine (5.87 g, 17.1 mmol) MS ESI: [M+H]+ m/z 344.1. 1H NMR (500 MHz, DMSO-d6) δ 9.50 (s, 1H), 838 (d, J=1.6, 1H), 7.81-7.62 (m, 2H), 7.07 (s, 1H), 2.36 (d, J=2.3, 3H), 2.26 (s, 3H), 1.27 (s, 12H).

後処理

  1. temperatureThe mixture was cooled to room temperature
  2. extractionextracted with ethyl acetate
  3. washThe organic extracts were washed with brine
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customPurification by flash chromatography

出典と根拠

ORDレコード
ord-d6a3f5970a0449208fef03f18bbfd0bc
出典データセット
uspto-grants-2013_10
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08551984B2

反応ノート

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